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C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone

C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene

A—HUMAN NECESSITIES

A23—FOODS OR FOODSTUFFS; THEIR TREATMENT, NOT COVERED BY OTHER CLASSES

A23K—FODDER

A23K20/00—Accessory food factors for animal feeding-stuffs

A23K20/10—Organic substances

A23K20/179—Colouring agents, e.g. pigmenting or dyeing agents

A—HUMAN NECESSITIES

A23—FOODS OR FOODSTUFFS; THEIR TREATMENT, NOT COVERED BY OTHER CLASSES

A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A23B - A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL

A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor

A23L5/40—Colouring or decolouring of foods

A23L5/42—Addition of dyes or pigments, e.g. in combination with optical brighteners

A23L5/43—Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives

A23L5/44—Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives using carotenoids or xanthophylls

Abstract

A process to obtain a product having a high content of zeaxanthin, lutein
or mixtures thereof, as short chain organic acid diesters of zeaxanthin, lutein or
mixtures thereof, that can be used mainly for the pigmentation of broilers and
egg yolks, as well as an intermediate in the cantaxanthin (β,β-Carotene-4,4'-dione)
and astaxanthin (3,3'-Dihidroxy β,β-carotene,4,4'-dione) synthesis, by
reacting extracts obtained from marigold (Tagetes Erecta L.), or plant extracts
that contain lutein, zeaxanthin or mixtures thereof in any proportion, with acetic
or propionic anhydride under controlled conditions of temperature and
pressure.

Description

BACKGROUND OF THE INVENTIONA. FIELD OF THE INVENTION

[0001]

This invention is related to short chain diesters, and more particularly to a
process for the obtain a product with a high content of zeaxanthin, lutein or
mixtures thereof, as short chain organic acid diesters of zeaxantine, lutein or
mixtures thereof.

B. DESCRIPTION OF THE RELATED ART.

[0002]

The yellow carotenoids such as the lutein and the zeaxanthin, occur in
marigold flowers as mono- or diesters, linked to long chain fatty adds such as
palmitic, stearic or myristic acids, among others (Alam, A. U. (1968) Lipids,
3(2), 183; Gayle G. (1986)J. Food Sci., 51(4), 1093).

[0003]

It is assumed that in such chemical structure, the carotenoids are better
protected against oxidative processes, so that the flower color is better
preserved in nature.

[0004]

However, in the pigmentation of broilers, it has been shown that the
bioavailability of such carotenoid fatty esters is lower than when they are
hydrolized, i.e. when they are fed as free carotenoids (Coon, C.N. (1976) Poult.
Sci., 55, 841-847).

[0005]

Applicant's have found that by saponification of the marigold carotenoids
and their subsquent linking to short chain organic acids, such as formic, acetic
propionic, etc., an improvement in their bioavailability, and that a more stable
form of the carotenoids is achieved.

[0006]

The acetylation of carotenoids, zeaxanthin among others, has been
carried out in laboratory scale since decades ago. The reported methodology
specifically refers to a research, for elucidation purposes about the chemical
structures of the carotenoids.

[0007]

The carotenoid in pure form, zeaxanthin in this case, is dissolved in
pyridine treating it with acetic anhydride and agitation at room temperature to
obtain the acetylated derivative after several hours (Liaaen-Jensen, S. and
Jensen, A. (1971) Methods Enzymol. 23, 586), or in a few minutes if the
reactants mixture is maintained under reflux (Alam, 1968).

[0008]

Another preferred chemical path to obtain the acetylated compound is to
dissolve the zeaxanthin in pyridine and benzene to carry on the reaction at 20°
C with acetyl chloride, a few minutes later (Bartlett, L. (1969) J. Chem. Soc. C,
2538).

[0009]

In the process according with the present invention, marigold extracts
containing saponified and isomerized carotenoids (Torres, et al. 5,523,494
6/1996, 568/834), are treated directly with acetic anhydride, or propionic
anhydride in such a way as to obtain the short chain organic acid diester
derivatives of zeaxanthin, lutein or mixtures thereof, present in such extracts.

SUMMARY OF THE INVENTION

[0010]

It is a main objective of the present invention to provide a product having
a high content of zeaxanthin, lutein or mixtures thereof, in the form of short
chain organic acid diesters of zeaxanthin, lutein or mixtures thereof, which can
be used mainly in the pigmentation of broilers skin and egg yolks.

[0011]

It is an additional main objective of the present invention to provide a
process to obtain a product with a high content of zeaxanthin, lutein or mixtures
thereof, in the form of short chain organic acid diesters of zeaxanthin, lutein or
mixtures thereof which can be used mainly in the pigmentation of broilers skin
and egg yolks.

[0012]

It is still a main objective of the present invention to provide a process at
the above disclosed nature, by reacting short chain organic anhydrides to
saponified extracts containing carotenoids, in an inert atmosphere of carbon
dioxide, nitrogen or a mixture of born under controlled conditions of temperature
and pressure.

[0013]

It is another main objective of the present invention to provide a process
of the above disclosed nature in which saponified extracts containing
carotenoids are treated without the need to add of any solvent at all.

[0014]

It is still another main objective of the present invention, to provide a
process of the above disclosed nature, wherein the product or its formulations
can be used for the pigmentation of broiler skin and egg yolk or as a pigmenting
agent in aquaculture.

[0015]

It is also an additional object of the present invention to provide a
process of the above disclosed nature wherein the zeaxanthin diester obtained
can be used as an intermediate in the synthesis of astaxanthin or cantaxanthin.

[0016]

These and other objectives and advantages of the present invention will
be apparent to those persons having ordinary skill in the art, from the following
detailed description of the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0017]

The chemical process is carried out according to the following reaction:

[0018]

The saponified marigold extract containing the zeaxanthin, has been
obtained according to the procedure reported by Torres, et al. (1996), but any
pigmenting formulation or extract containing zeaxanthin can be used.
Regardless of the raw material employed, it should preferably be moisture free
before acetylating with acetic anhydride, or before treatment with propionic
anhydride.

[0019]

The carotenoid containing substrate is maintained at a temperature in the
range of 25°C to 140°C, but preferably between 40°C and 100°C.

[0020]

When a crude marigold extract containing the saponified and isomerized
carotenoids, enters into the reaction with the acetic or propionic anhydride, its
residual fatty acids and other lipids present occur as the sodium or potassium
.salts.

Acetylation reaction

[0021]

The acetic anhydride is slowly added to the extract in a reaction vessel
under agitation, in a proportion from 0.2 to 2.0 parts by weight for one part of
the pigmenting concentrate, which is in the form of a sodium or potassium soap
(a heavy paste highly soluble in water). The reaction mixture is partially soluble
in the acetic anhydride. However, as the acetylation reaction advances, an oily
phase separates from the reaction media, mainly composed of acetic acid and
sodium or potassium acetates in aqueous solution, from which it easily
separated by decanting. The acetylation vessel wherein the reaction takes
place should be kept under an inert atmosphere, in order to avoid the intensive
degradation of the xanthophylls. An inert diluent such as ethylene glycol or
propylene glycol or an aliphatic or cyclic hydrocarbon can be used to reduce the
viscosity of the mixture.

[0022]

The reaction time depends on the temperature and can be from 6
minutes to 24 hours, but preferably from 4 to 18 hours.

Parameter

Trial 1

Trial 2

Trial 3

Trial 4

Acetic anhydride: extract Ratio

0.5

2.5

1.0

2.0

Reaction time, hrs.

16

16

20

12

Reaction temperature, °C

90

80

100

60

Pressure, mm Hg

750

760

750

760

Mono-hydroxycarotenoids %

4.2

1.5

1.7

2.8

Di-hydroxycarotenoids %

2.1

1.3

1.3

0.8

Aceto-carotenoids %

88.5

91.8

89.6

90.2

Propionation reaction

[0023]

Propionic anhydride is slowly added to the extract in a reaction vessel
under agitation, in a proportion from 0.2 to 3.0 parts by weight to one part of the
pigmenting concentrate, which is in the form of sodium or potassium soap (a
heavy paste highly soluble in water). The reaction mix is partially soluble in the
propionic anhydride. However as the propionation reaction advances, an oily
phase separates from the reaction media, mainly composed of propionic acid
and sodium or potassium propionates in aqueous solution, from which it is
easily separated by decanting. The reaction vessel should be kept under an
inert atmosphere to avoid degradation.

[0024]

The reaction time depends on the temperature and can be from 5
minutes to 24 hours, but preferably from 3 to 17 hours.

Parameter

Trial 1

Trial 2

Trial 3

Trial 4

Propionic Anhydride:extract Ratio

0.8

2.5

2.0

3.0

Reaction time, hrs.

6

4

4

3

Reaction temperature, °C

70

60

80

80

Pressure, mm Hg.

760

780

760

750

Mono-hydroxycarotenoids %

4.1

1.5

1.8

0.7

Di-hydroxycarotenoids %

2.3

1.0

0.6

1.0

Propionate-carotenoids

86.0

90.0

89.0

91.0

[0025]

The saponified extracts used as the raw material in the above described
process, contain approximately 92 % of di-hydroxy carotenoids, and 1-2% of
mono-hydroxy carotenoids, quantified according to the AOAC method.

[0026]

The identification and quantification of the pigments involved were
carried out following the HPLC techniques mentioned by Torres, et al.( 1996),
as well as by the use of other spectroscopic techniques as IR, UV, 1HNMR, etc.,
widely used in carotenoids identification.

[0027]

The end product can be formulated as an aqueous emulsion, or it can be
dispersed by means of a carrier to obtain pre-mixtures of a given concentration
of zeaxanthin, lutein or mixtures thereof in the form of short chain organic acid
diesters, to be used as a pigmenting agent for broiler's skin, egg yolks, or
shrimps and salmon in aquaculture.

Claims (27)

A process for the obtention of short chain organic acid diesters of mono-or
polyhydroxylated carotenoids, from saponified extracts containing
carotenoids, comprising: reading short chain organic anhydrides, slowly under
agitation, to said saponified extracts containing carotenoids, under controlled
conditions of temperature and pressure.

The process as claimed in claim 1, wherein the carotenoids are selected
from the group consisting in yellow carotenoids, lutein or zeaxhantin.

The process as claimed in claim 1, wherein the zeaxanthin is in its free
hydrolized form.

The process as claimed in claim 1, wherein the lutein or any other
hydroxycarotenoid or mixtures thereof are hydrolized.

The process as claimed in claim 1, wherein the short chain organic
anhydrides are selected from the group consisting of acetic anhydride or
propionic anhydride.

The process as claimed in claim 1, wherein the proportion of acetic
anhydride is from 0.2 to 2.0 parts by weight, preferably from 0.5 to 1.5 parts by
weight, for one part of extract.

The process as claimed in claim 1, wherein the proportion of propionic
anhydride is from 0.5 to 3.5 parts, preferably form .5 to 1.5 parts by weight for
one part of extract.

The process as claimed in claim 1, wherein the saponified extract is
preferably moisture free.

The process as claimed in claim 1, wherein the saponified extract is
from an alkaline reaction, containing residual NaOH, KOH or a mixture of both,
or any other alkaline or alkaline-hearth metal hydroxides, as well as organic
basis such as the morpholine, ethylamine, diethylamine, ethanolamine and the
like.

The process as claimed in claim 1, wherein the reaction is carried out in
the presence of ethylene glycol or propylen glycol in order to reduce the
viscosity of the mixture.

The process as claimed in claim 1, wherein the reaction is carried out in
the presence of an aliphatic or a cyclic hydrocarbon or an organic solvent to
reduce the viscosity of the mixture.

The process as claimed in claim 1, wherein the acetic anhydride can be
mixed in any proportion with metallic salts of acetic acid, preferably with sodium
or potassium salts.

The process as claimed in claim 1, wherein the propionic anhydride can
be mixed in any proportion with metallic propionates, preferably with sodium or
potassium salts.

The process as claimed in claim 1, wherein the reaction time is from 5
minutes to 12 hours, preferably from 2 to 10 hours.

The process as claimed in claim 1, wherein the reaction temperature is
from 25°C to 140°C, preferably from 40°C to 100°C.

The process as claimed in claim 1, wherein the reaction is carried out in
an inert atmosphere of carbon dioxide, nitrogen, or a mixture of both.

The process as claimed in claim 1, wherein the reaction product contains
from 5% to 90% of zeaxanthin diacetate.

The process as claimed in claim 1, wherein the reaction product
contains from 5% to 90% of zeaxanthin di-propionate.

The process as claimed in claim 1, wherein the product or its
formulations can be used for the pigmentation of broilers skin and egg yolks or
as a pigmenting agent in aquaculture.

The process as claimed in claim 1 wherein the zeaxanthin diester
obtained can be used as an intermediate in the synthesis of astaxanthin.

The process as claimed in claim 1 wherein the zeaxanthin diester
obtained can be used as an intermediate in the synthesis of cantaxanthin.

Short chain organic acid diesters of mono- or polyhydroxylated
carotenoids, of the formula:

The short chain organic acid diesters, as claimed in claim 23,
containing from 5% to 90% of zeaxanthin diacetate.

The short chain organic acid diesters, as claimed in claim 23, containing
from 5% to 90% of zeaxanthin di-propionate.

Short chain organic acid diesters of mono- or polyhydroxytated
carotenoids, obtained by reacting short chain organic anhydrides, slowly under
agitation, to saponified extracts containing carotenoids, under controlled
conditions of temperature and pressure.

The short chain organic acid diesters as claimed in claim 26, wherein the
short chain organic anhydrides are selected from the group consisting of acetic
anhydride or propionic anhydride.

EP199809583951997-11-251998-11-25Process for the production of short chain diesters
Not-in-forceEP1044954B1
(en)